Kinetics and Mechanism of Metal Nanoparticle Growth via Optical Extinction Spectroscopy and Computational Modeling: The Curious Case of Colloidal Gold
An overarching computational framework unifying several optical theories to describe the temporal volution of gold nanoparticles (GNPs) during a seeded growth process is presented. To achieve this, we sed the inexpensive and widely available optical extinction spectroscopy, to obtain quantitative kinetic data. In situ spectra collected over a wide set of experimental conditions were regressed using the hysical model, calculating light extinction by ensembles of GNPs during the growth process. This model rovides temporal information on the size, shape, and concentration of the particles, and any electromagnetic interactions between them. Consequently, we were able to describe the mechanism of GNP growth and divide the process into distinct genesis periods. We provide explanations for several longstanding mysteries, e.g., the phenomena responsible for the purple-greyish hue during the early stages of GNP growth, the complex interactions between nucleation, growth and aggregation events, and a clear distinction between agglomeration and electromagnetic interactions. The presented theoretical formalism has been developed in a generic fashion so that it can readily be adapted to other nanoparticulate formation scenarios such as the genesis of various metal nanoparticles.
